Copper-Catalyzed Cascade Synthesis of [1,2,4]-Triazoloquinazolinones

Zhenbang Lou; Ningning Man; Haijun Yang; Changjin Zhu; Hua Fu

doi:10.1055/s-0036-1591565

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(10): 1395-1399
DOI: 10.1055/s-0036-1591565

letter

Copper-Catalyzed Cascade Synthesis of [1,2,4]-Triazoloquinazolinones

Zhenbang Lou

^aSchool of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. of China eMail: fuhua@mail.tsinghua.edu.cn

^bKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

,

Ningning Man

^bKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

,

Haijun Yang

^bKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

,

Changjin Zhu

^aSchool of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. of China eMail: fuhua@mail.tsinghua.edu.cn

,

Hua Fu *

^aSchool of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. of China eMail: fuhua@mail.tsinghua.edu.cn

^bKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China

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Abstract

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Abstract

An efficient and practical method for the synthesis of 1,2,4-triazolo[5,1-b]quinazolin-9(3H)-ones has been developed via the copper-catalyzed domino reactions of readily available substituted N′-acetyl-2-bromobenzohydrazides with cyanamide. The protocol uses inexpensive CuI as the catalyst, and no other ligand or additive was required. The target products were prepared in good to excellent yields with tolerance of various functional groups.

Key words

copper - domino reactions - [1,2,4]-triazoloquinazolinones - cyanamide - synthetic method

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Referenzen

References and Notes

1a Landquist JK. In Comprehensive Heterocyclic Chemistry . Katritzky AR. Rees CW. Pergamon; New York: 1984
1b Crowley PJ. In Comprehensive Heterocyclic Chemistry . Katritzky AR. Rees CW. Pergamon; New York: 1984

2 Leeson PD. Springthorpe B. Nat. Rev. Drug Discovery 2007; 6: 881

3a Shiba SA. El-Khamry AA. Shaban ME. Atia KS. Pharmazie 1997; 52: 189
3b Pandeya SN. Sriram D. Nath G. De Clercq E. Pharm. Acta Helv. 1999; 74: 11

4a Bartroli J. Turmo E. Alguero M. Boncompte E. Vericat ML. Conte L. Ramis J. Merlos M. Garcia-Rafanell J. Forn J. J. Med. Chem. 1998; 41: 1869
4b Bereznak JF. Chang ZY. Sternberg CG. PCT Int. Appl WO 9702262, 1997
4c Bereznak JF. Chang ZY. Selby TP. Sternberg CG. U.S. Patent US 5945423, 1999

5a Bekhit AA. Khalil MA. Farmaco 1998; 53: 539
5b Santagati NA. Bousquet E. Spadaro A. Ronsisvalle G. Farmaco 1999; 54: 780

6 Skelton L. Bavetsias V. Jackman A. PCT Int. Appl WO 0050417, 2000

7a Welch WM. Ewing FE. Huang J. Menniti FS. Pagnozzi MJ. Kelly K. Seymour PA. Guanowsky V. Guhan S. Guinn MR. Critchett D. Lazzaro J. Ganong AH. Devries KM. Staigers TL. Chenard BL. Bioorg. Med. Chem. Lett. 2001; 11: 177
7b Chenard BL. Menniti FS. Welch WM. Jr. Eur. Patent EP 900568, 1999

8a Dickinson RP. Bell AW. Hitchcock CA. Narayana-Swami S. Ray SJ. Richardson K. Troke PF. Bioorg. Med. Chem. Lett. 1996; 6: 2031
8b Dickinson RP. Bell AW. Hitchcock CA. Narayana-Swami S. Ray SJ. Richardson K. Troke PF. Bioorg. Med. Chem. Lett. 1996; 6: 2031
8c Mikamo H. Yin XH. Hayasaki Y. Satoh M. Tamaya T. Chemotherapy 2001; 47: 377
8d Ulusoy N. Gursoy A. Otuk G. Farmaco 2001; 56: 947
8e Nagai S.-I. Takemoto S. Ueda T. Mizutani K. Uozumi Y. Tokuda H. J. Heterocycl. Chem. 2001; 38: 1097
8f Palaska E. Sahin G. Kelicen P. Durlu NT. Altinok G. Farmaco 2002; 57: 101

9a Giri S. , Nizamuddin, Singh KK. Indian J. Chem., Sect B 1982; 21: 377
9b Westwood R. Tully WR. Murdoch R. Eur. Parent EP 34529, 1981

For selected papers, see:

10a El-Brollosy NR. Abdel-Megeed MF. Genady AR. Monatsh. Chem. 2001; 132: 1063
10b El-Hiti GA.-R. Bull. Chem. Soc. Jpn. 1997; 70: 2209
10c Kottke K. Kuehmstedt H. Pharmazie 1985; 40: 55
10d Hussein MA. Med. Chem. Res. 2012; 21: 1876

11 Ding M.-W. Chen Y.-F. Huang N.-Y. Eur. J. Org. Chem. 2004; 3872

For selected reviews on copper-catalyzed cross-couplings, see:

12a Ley SV. Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400
12b Beletskaya IP. Cheprakov AV. Coord. Chem. Rev. 2004; 248: 2337
12c Evano G. Blanchard N. Toumi M. Chem. Rev. 2008; 108: 3054
12d Ma D. Cai Q. Acc. Chem. Res. 2008; 41: 1450
12e Monnier F. Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 6954
12f Surry DS. Buchwald SL. Chem. Sci. 2010; 1: 13
12g Rao H. Fu H. Synlett 2011; 745 ; and references cited therein

13a Liu X. Fu H. Jiang Y. Zhao Y. Angew. Chem. Int. Ed. 2009; 48: 348
13b Huang C. Fu Y. Fu H. Jiang Y. Zhao Y. Chem. Commun. 2008; 6333
13c Yang D. Fu H. Hu L. Jiang Y. Zhao Y. J. Org. Chem. 2008; 73: 7841
13d Yang D. Liu H. Yang H. Fu H. Hu L. Jiang Y. Zhao Y. Adv. Synth. Catal. 2009; 351: 1999
13e Wang F. Liu H. Fu H. Jiang Y. Zhao Y. Org. Lett. 2009; 11: 2469
13f Lu J. Gong X. Yang H. Fu H. Chem. Commun. 2010; 46: 4172
13g Yang X. Fu H. Qiao R. Jiang Y. Zhao Y. Adv. Synth. Catal. 2010; 352: 1033
13h Gong X. Yang H. Liu H. Jiang Y. Zhao Y. Fu H. Org. Lett. 2010; 12: 3128
13i Wang C. Li S. Liu H. Jiang Y. Fu H. J. Org. Chem. 2010; 75: 7936
13j Yang D. Wang Y. Yang H. Liu T. Fu H. Adv. Synth. Catal. 2012; 354: 477
13k Lou Z. Wu X. Yang H. Zhu C. Fu H. Adv. Synth. Catal. 2015; 357: 3961

14a Martin R. Rivero MR. Buchwald SL. Angew. Chem. Int. Ed. 2006; 45: 7079
14b Martín R. Larsen CH. Cuenca A. Buchwald SL. Org. Lett. 2007; 9: 3379
14c Zou B. Yuan Q. Ma D. Angew. Chem. Int. Ed. 2007; 46: 2598
14d Ma D. Cai Q. Acc. Chem. Res. 2008; 41: 1450
14e Evindar G. Batey RA. J. Org. Chem. 2006; 71: 1802
14f Bonnaterre F. Bois-Choussy M. Zhu J. Org. Lett. 2006; 8: 4351
14g Altenhoff G. Glorius F. Adv. Synth. Catal. 2004; 346: 1661
14h Liu T. Fu H. Synthesis 2012; 44: 2805 ; and references cited therein

15 General Procedures for the Preparation of Compounds 3a–w: A Schlenk tube was charged with a mixture of CuI (0.03 mmol, 5.7 mg), Cs₂CO₃ (0.3 mmol, 98 mg), substituted N′-acetyl-2-bromobenzohydrazide 1 (0.3 mmol), cyanamide (2; 0.45 mmol, 19 mg) and anhyd DMF (3.0 mL). After being evacuated and recharged with Ar for three times, the tube was sealed and the mixture was allowed to stir at 120 °C for 10–15 h. After completion of the reaction, the mixture was cooled to r.t., and H₂O (20 mL) was added to the mixture. The solution was extracted with CH₂Cl₂–MeOH (10:1; 3 × 10 mL), and the combined organic layers were dried over anhyd Na₂SO₄. The solution was concentrated, and the residue was purified by silica gel column chromatography (CH₂Cl₂–MeOH = 30:1 or 20:1) providing the target product (3a–x). Three representative examples are shown as follows: 6-Methyl-2-phenyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3e): eluent: CH₂Cl₂–MeOH = 30:1. Isolated yield: 85% (70.4 mg); white solid; mp 352–353 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.16 (d, J = 6.5 Hz, 2 H), 8.11 (d, J = 8.2 Hz, 1 H), 7.54 (q, J = 6.4 Hz, 3 H), 7.27 (s, 1 H), 7.21 (d, J = 8.2 Hz, 1 H), 2.47 (s, 3 H). ¹³C NMR (151 MHz, DMSO-d₆ ): δ = 161.6, 155.4, 151.5, 145.9, 139.5, 130.4, 130.1, 128.9 (2 × CH), 127.4, 126.7 (2 × CH), 124.4, 116.3, 111.3, 21.6. ESI–HRMS: m/z [M + Na]⁺ calcd for C₁₆H₁₂N₄NaO: 299.0903; found: 299.0906. 7-Chloro-2-phenyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3r): eluent: CH₂Cl₂–MeOH = 30:1. Isolated yield: 68% (60.4 mg); white solid; mp 281–283 °C. ¹H NMR (600 MHz, DMSO-d ₆): δ = 8.14–8.19 (m, 3 H), 7.88 (dd, J = 8.8, 2.4 Hz, 1 H), 7.51–7.58 (m, 4 H). ¹³C NMR (151 MHz, DMSO-d ₆): δ = 161.6, 155.0, 151.3, 139.1, 134.5, 131.1, 129.9, 128.3 (2 × CH), 127.9, 127.1, 126.5 (2 × CH), 122.4, 116.6. ESI–HRMS: m/z [M + H]⁺ calcd for C₁₅H₁₀ClN₄O: 297.0538; found: 297.0540. 2-Methyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3w): eluent: CH₂Cl₂–MeOH = 30:1. Reaction time: 15 h. Isolated yield: 67% (40.3 mg); white solid; mp 312–314 °C. ¹H NMR (600 MHz, DMSO-d ₆): δ = 8.16 (d, J = 7.7 Hz, 1 H), 7.78 (t, J = 7.4 Hz, 1 H), 7.50 (d, J = 7.9 Hz, 1 H), 7.33 (t, J = 7.5 Hz, 1 H), 2.36 (s, 3 H). ¹³C NMR (151 MHz, DMSO-d ₆): δ = 161.9, 155.2, 151.0, 139.7, 134.8, 127.3, 122.6, 117.2, 113.3, 14.4. ESI–HRMS: m/z [M + H]⁺ calcd for C₁₀H₉N₄O: 201.0771; found: 201.0770.

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